p-phenylenediamines containing alkylacylamidoethyl or alkylacylamidoethoxy ring substituents



Patented May 8, 1951 UNITED STATES PATENT OFFICE p-PHENYLENEDIAMINESCONTAINING AL- KYLACYLAMIDOETHYL OR ALKYLACYL- AMIDOETHOXY RINGSUBSTITUENTS Arnold Weissberger, Dudley B. Glass, and Paul W. Vittum,Rochester, N.'Y., assignors to Eastman Kodak Company, Rochester, N. Y.,a corporation of New Jersey No Drawing. Original application March 6,1948,

Serial No. 13,526. Divided and this application March 18, 1949, SerialNo. 82,282

pounds for producing fine grain black and white photographic images andalso that these compounds, especially when they contain alkylsubstituents on one of the nitrogen atoms, are useful as developers inproducing colored photographic images. A serious disadvantage of thep-phenylenediamine developers is that they are highly allergenic, thatis, they are poisonous to the human skin and are therefore somewhatdangerous to use.

The allergenic properties of the p-phenylenediamine developers may beovercome by substituting a sulfonamide group or an amine sulfonyl groupin the alkyl group on the nitrogen atom of p-phenylenediamine asdescribed in Weissberger U. S. Patent 2,193,015, granted March 12, 1940.These substituted p-phenylenediamine developers, however, are sometimestoo low in developing strength (or reduction poteninvention by the useas developing agents of compounds of the following general formulas:

2 and o CHzCHgNHX where R is a lower alkyl group such as methyl, ethylor propyl, R is a lower alkyl group, X is the substituted acyl group-SO2R" or -COR" and R is a lower alkyl group.

By lower alkyl group, we mean a methyl,

ethyl or propyl group.

Compounds of this class which may be used according to our invention areas follows:

1 CHHB 2 5 OH CH NHO 00H;

NH; 3- (B-a cetamidoethyl) 4-amino-N,N-diethylaniline 2 C 2H5 C 2B5OHQCHzNHSOgOHa 4-amino-N,N-diethyl-3-(B-methyl-sulfonamidoethyl)-aniline 3-(B-acetamidoethoxy)-4-am1no-N,N-diethylanil1ne 4 C:H| CIHB Thespecific compounds illustrated above were prepared as follows:

1. 3 (p acetamidoethyl) 4 amino N,N diethylaniline was prepared from3-nitrotoluene a by the followin series of reactions.

11. 3-nitrobenzyl briomide.-3-nitrotoluene (5 moles) was heated at 135i5and bromine (5 H, moles) was dropped in during a period of 5 4-amin-N,N-diethy1-3-,(fi-methylsulfonamidoetho y)- h During, this time ereaction mixture aniline 10 was exposed to the lightiofa, 200 w; clearbulb. The reaction mixture was cooled, dissolved in ether and the etherwas dried over anhydrous O CH2CHINHSO2CHI The preparation of ourdevelopers may be summarized by the following reaction schemes:

NO NH;

sodium sulfate. The ether wa evaporated and the residue was distilledunder reduced pressure collecting the fraction that boiled at 120-150/2mm. This crude product was redistilled under reduced pressure collectingthe portion that boiled at 160-162/14 mm. This redistilled material wasrecrystallized from methanol and dried in air. Melting point 58-59".

I). 3-nitrophenylacetonitrile.-Sodium cyanide (1.0 mole) was dissolvedin 80 ml. of water. Alcohol (280 ml.) was added and the mixture wascooled to 20. 3-nitrobenzyl bromide (0.8 mole) was added and the mixturewas stirred and warmed slowly to 40. At this temperature the heating wasstopped and the exothermic reaction allowed to proceed. The temperaturewas not allowed to rise above 60-65. After the spontaneous reaction wasover, the reaction mixture was boiled for 1 hour. The alcohol wasremoved under reduced pressure and the residue was dissolved in 250 ml.of water plus 300 ml. of ether. The layers were separated, and the etherlayer was washed with water and dried over anhydrous sodium sulfate. Theether was evaporated and the residue was distilled under reducedpressure collecting the fraction that boiled at 160165/3 mm. The productwas recrystallized from methanol. Melting point 61-62". A

c. 3 aminophenylacetonitrile. 3 nitro-' phenylacetom'trile (0.9 mole)was added to a solution of stannous chloride (2.7 moles) in concentratedhydrochloric acid (700 ml.). The temperature of the reaction mixture wasmaintained at 35-40, by cooling, until the exothermic reaction subsided.After stirring for 2 hours, the solution was made alkaline with 2 l. of40 per cent sodium hydroxide solution. This mixture was diluted with 1l. of water and the product extracted with ether. The ether solution waswashed with water, dried over anhydrous sodium sulfate and the ether wasevaporated. The residue was distilled under reduced pressurecollectingthe fraction that boiled at 132-135/2 mm.

d. 3-(N,N-diethylamzfno) phenylacetom'trile. A mixture of3-amino-phenylacetonitrile (0.75 mole), alcohol (400 ml.), sodiumcarbonate (1.0 mole), water (100 ml.) and ethyl iodide (1.8 moles) wasboiled under reflux for 6 hours. The alcohol was removed under reducedpressure and the residue was dissolved in a mixture of water (500 ml.)and ether (500 ml.). The ether layer was separated, washed with waterand dried over anhydrous sodium sulfate. The ether was evaporated andthe residue was distilled under reduced pressure collecting the fractionthat boiled at 125130/2 mm.

e. 3 (p aminoethyl) N,N-diethyZaniline.-- 3 (N,N diethylamino)-phenylacetonitrile (0.66 mole) was placed in a high pressure reductionapparatus with liquid ammonia (250 ml.) and methanol (150 ml.) andhydrogenated at 110 in the presence of Raney nickel (10 g.) and ahydrogen pressure of 1500 lbs./in. The product was distilled underreduced pressure collecting therfraction that boiled at 148-150/10 mm.

1. 3 (,6 acetamidoethyl) 4 amino N,N- diethyZam'Zine.-3 (13 amino ethyl)N,N- diethylaniline (0.39 mole) was addedwith stirring and cooling to 40n11. of acetic anhydride. The mixture was kept below a temperature of 50during the addition and then was heated on the steam bath for 30minutes. After cooling, the solution was stirred with 400 ml. of wateruntil the excess acetic anhydride had decomposed. The solution was madeacid with 100 m1. of concentrated hydrochloric acid, cooled to 0, andnitrosated by the addition of a. solution of 28 g. of sodium nitrite in50 ml. of water. The nitrite was added during a period of 1 hour.Stirring was continued for 1 hour longer at 0. This solution was furtheracidified by the addition of ml. of concentrated hydrochloric acid andthe nitroso compound was reduced with 65 g. of zinc dust. The zinc dustwas added in portions, with stirring, while the temperature of thereaction mixture was maintainedat 15:5". The excess zinc dust wasfiltered off and the solution was made alkaline with 400 ml. of ammoniumhydroxide. The diamine was extracted with 600 ml. of chloroform. Thechloroform solution was washed with water and dried over anhydroussodium sulfate. The chloroform was removed under reduced pressure andthe diamine was distilled under reduced pressure. The portion thatboiled at 190-195 at 1 mm. was collected as the desired product.

2. 4 amino-N,N-diethyl 3 (,B-methylsulfonamidoethyl) aniline wasprepared from 3-(-.B- aminoethyl) N,N-diethylaniline by the followingmethod.

A mixture of 3-(fl-aminoethy1)-N,N-diethylaniline (0.36 mole) and water(150 ml.) was cooled to 15 and stirred vigorously while methanesulfonylchloride (0.41 mole) was dropped in during the course of 30 minutes.After each fifth of the methanesulfonyl chloride had been added,one-fifth of a solution of sodium hydroxide (0.41 mole) in water (50ml.) was added. The temperature was held at 15-20 throughout theaddition. The mixture was stirred for 2 hours at room temperature andthen extracted with ch10 roform. The chloroform solution was washed withwater, dried over anhydrous sodium sulfate and the chloroform Wasevaporated under reduced pressure. The residue was dissolved in amixture of ml. of concentrated hydrochloric acid and 400 ml. of water,and nitrosated at 0 by the addition of 22.5 g. of solid sodium nitriteduring a period of 1 hour. The mixture was stirred for 1 hour at 05 andthen made alkaline with ammonium hydroxide. The mixture was stirredthoroughly and the aqueous portion was decanted from the gummy product.The gum was washed with water and dissolved in a mixture of 166 ml. ofconcentrated hydrochloric acid and 400 ml. of water. This mixture wascooled to 15 and zinc dust (1 mole) was added in portions with stirring,keeping the temperature below 20. The excess zinc was removed byfiltration and the filtrate made alkaline with ammonium hydroxide. Thediamine was extracted with chloroform. The chloroform solution waswashed with water, dried over anhydrous sodium sulfate and thechloroform was removed under reduced pressure. The residue was distilledunder reduced pressure. The fraction that boiled at 215220/ 1 mm. wascollected as pure product.

3. 3 (B-acetamidoethoxy) 4 amino-N,N-diethylaniline was prepared by thefollowing series of reactions.

a. 3 (.fl-chZoroetho-xy) -N,N-diethyZaniline.-A solution of 80 g. ofsodium hydroxide in 2 1. of water was placed in a flask and melted3-(N,N- diethylamino) phenol (3 moles) was added and the mixture washeated on a steam bath for 19 hours with stirring. At the end of thisperiod the mixture was cooled and ml. of 40% sodium hydroxide solutionwas stirred in. The solution was extracted twice with ether. The

7: ether solution.waswashedwith water, dried-over. anhydrous.-;sodiumsulfate. and; the ether was evaporated; Theoresidudwas distilledunderzreduced pressure The: product boiled at 125-135 at'2.mm.

b: N-,N.- Methyl-. 3 (fi phthalimidoethoxy) amline.zA- mixture of3-(fi-chl0roethoxy9 -N,=Ndiethylaniline. (1.01 moles), potassiumphthalate (1.07 moles) and; diethyleneglycol' (2 1.) was stirred slowlyandheated at--1.40-150 for hours. Thexsolution was poured into 1 l. ofcoldwa-ter and allowed to standfor 10-12 hours at 0. The precipitate;was. removed by filtration, washed with alcohol and recrystallized froma mixture of 850 ml; of 3A and 760 ml. of ethylacetate; T-hepro ductmeltedat 127--129.

c. 3- (fi-ammoerhorys).-N,N-diethyZaniZme:-A mixtureofN,Na-diethyl-3-'(d+phthalimidoethoxy.) aniline (0.43 mole), 85%hydrazine (0.43 mole) and 300ml.- of alcohol was boiled under reflux for30.:minutes. The mixture was cooledsomewhat and 140 ml. of concentratedhydrochloric acid was added. The mixture was then boiled under refluxfor 30 minutes, cooled and'diluted with -'750 ml. of water. Thehydrazide was filtered off and the filtrate was concentrated underreduced pressure until the alcohol had been removed. Thearesidue-wasmade alkaline with ammonium' hydroxide. The amine. was: extracted withether. The ether" solution was-dried over anhydrous sodium sulfate andthe ether was evaporated. Theresidue was'distilled under reducedpressure. The product boiled at 135-142 at 2 mm.

d. 3 (,8 acetamz'doethoxw N,N diethylaniline.3 3 aminoethoxy) N,N-diethylaniline (0.07) was added to 15 ml. of acetic anhydride and thesolution was heated on a steam bath for 30 minutes. The solutionwas-stirred with 70 ml. of water until the excess anhydride haddecomposed and then was concentrated to a thick syrup under reducedpressure: The syrup. was dissolved in 150 ml. of boiling ligroin. Theligroin solution was filtered while stillhot'and allowed to cool. Thecrystals were removed by filtration and dried in air. Melting point66.5-67".

e; 3- (,Beaceiamidoethoazy) -N,N-diethyZ-4-m'trosoaniline.3 (oacetamidoethoxy) -N,N-diethylaniline (0.07 mole) was dissolved in 140ml.of water and'21 ml. of concentratedhydrochloric acid. The solution wascooled to 0 and nitrosated with a solutionof 5.0 g. of sodium nitrite in35 ml. of water. After standing at 0 for minutes the reaction mixtureWas made alkaline with ammonium hydroxide and the nitroso compound .Wasextracted with chloroform. Thechloroform solution was driedoveranhydrous-sodium sulfate and then the chloroform was removed underreduced pressure keeping the temperature of the nitroso compound at20-25". The nitroso compound after" recrystallized from :benzene meltedat l24124.5.

f. 3- (.fi-acetamidoethoxy) -4-a.mino -N,N-di'eth ylaniline.3(B-acetamidoethoxy) -N,N-diethyl- 4-nitrosoaniline (0:06 mole) and.50ml. of absolute alcohol were placed in a Parr hydrogenationapparatus-andreduced in the presenceof Raney nickel at a' temperature of60 and a hydrogenpressure of 3 atmospheres. Theca-talyst was re-' movedby filtration and the alcohol wasevaporated under reduced pressure. Theresidue was distilled under reduced pressure. The portion that boiled at112 11? at 1 mm. was diluted with 25 ml. of petroleum ether. Aiterstanding at 0 for. 16 hourskthe product. wasfiltered ofitanfi 8 dried;in: a: vacuum desiccator. 50-51";

4. 4'-- amino -N,N diethyl;3-(fi-methylsulfonamidoethoxyl-aniline wasprepared from 34paminoethoxy) -N,N-diethylaniline by thefollowingniethodz.

a; N,N-- diethyl -3 (,8-methylsuljonamidoeth- 0wy)aniZine.A mixture of3-(B-aminoethoxy)- N,N-diethylaniline; (0.1 mole) and 40 ml. .of waterWas cooled to 1520 and stirred while 9 m1. of :methanesulfonyl chloridewas added slowly. After. each quarter of the acid: chloride had beenadded,..one-fourth of'a So1ution'of'4-.5 g. of sodium hydroxide in 15ml. of water was-added. The temperature ofthe reaction mixture was maintaine'd-at 15--20 during the reaction- After stirring at 20 for twohours, theprecipitate was .removed by filtrationand recrystallized:from: ml. Of'45 aqueousalcohol. After drying. in air, the product melted:at- 70-72".

D. N,N- diethyl- --3- (ii-methylsulfonamidoeth 0mg)-4-'-nitrosoam'line-.A solution of N ,N dieth yl-3-(fi-methylsulfonamidoethoxy) 'anilin'e' (0.058 mole) in 50ml. of: waterand 17 ml. of concen trated hydrochloric acid was cooled to 0 andnitrosatedby the addition ofa-solution of4.1 g; of sodiumzni-trite111.15 ml. of-water. The solution 'waststirred at. 0? *for minutes,dilutediwith 50 ml. of water and made alkaline with1ammonium hydroxide.The. precipitate: was removed by filtration and:recrystallizedzfromr100ml..of 50% aqueous alcohoL. Thetproduct was dried in air.

c. 4- ami'no NgN- Methyl-3 .-(p-methylsuljonamidoethoxy)aniZine.-N,N-diethyl-3-(flamethyls'ulfonamid'oethoxy) 4 nitrosoaniline(0.0365 mole) and .75 ml. of absolute alcohoLw'ereiplac'ed inv a Pair:hydrogenation apparatus andreduced in theipresence of :Raney: nickel ata temperature of? andlahydrogenzpressure.of .3 atmospheres. Thecatalystiwasmemoved by filtration and the filtrate. was: concentrated toa syrup underreducedpressurez The residue was-recrystallized fromaqueousalcohol. The produczt, dried'in a vacuni'desiccator, melted'at 89-01Whenlused for .the=.formation of colored 'photo graphic: images,.. thedevelopers of our in'- vention.v may. be used in conjunctionwith anywell ekno-wnicou-plerl compoundssuch as thosedescribeddn Fisher U. .S;Patent '1,'102,028, grantedJune 30, 1914, .Mannesand Godowsky-U. S5Patent 2,100,602, granted Fe'bruary' w, 1938; or Marines; .Godowsky. andPeterson U. 6. Patents 2,115,394,. granted: April 26',- 1933, and2,126,337, granted August 9, 1938.

Thetfollowing exampleillustrates a developingsolution which may beusedaccordingto -our invention.

Melting; point 4a- -amino-N;N-diethyl -3 (B=m'ethylsulfona-midoethylaniline grams 2.5

Sodium sulfite' do' 2 Sodiumcarbonate" do-' 30 Potassiumbromide do 2Waterto l-liter Coupler (o-phenylphenol) do 2 Sodium hydroxide(10%.solution) cc 20 F0r-use,-B isadded to A;

The developing agents described in' the present application maybeused'to form photographic images by'development ofexposed'silvei' halidecontained-in the usual gelatin carrier r-hrcarrierssuch:ascollodiontwater-permeablecellulose 9 i 10 ester orwater-permeable synthetic resins. Our 4. An amino compound having theformula developing agents may be used with photographic R filmscontaining the coupler in the emulsion layer as described in Mannes andGodowsky U. S. Patent 2,304,940, granted December 15, 1942, or Jelleyand Vittum U. S. Patent 2,322,027, granted June 15, 1943. When used inthis way, a developing solution similar in composition to Part A inOOHCHNHBOR the above example is suitable. NH It will be understood thatthe examples included herein are illustrative only and that our in-Where R and are lower. alkyl groups vention is to be taken as limitedonly by the scope An ammo compound having the formula of the appendedclaims.

We claim: 02H: C255 1. An amino compound having a formula of N the classconsisting of omomNHooom NH: CHCHNHX 6. An amino compound having theformula 0 H c H and 2 5/ 2 5 R\ /R N 80 CHiCHjNHSO CHg O 0 H10 HiNHX NH:

NH 7. An amino compound having the formula where R and R are lower alkylgroups, X is CHE 01H selected from the class consisting of SO2R" andCOR" groups, and R" is a lower alkyl N group.

2. An amino compound having the formula R\ /R1 ocmcmunsoicm ARNOLDWEISSBERGER. CH CH NHSO RII B. I PAUL W. VI'ITUM. NH: Where R, R and R"are lower alkyl groups. REFERENCES CITED An ammo compound havmg theformula The following references are of record in the file of thispatent:

N/ UNITED STATES PATENTS Number Name Date 2,193,015 Weissberger Mar. 12,1940 CECHNHCOR" 2,304,953 Peterson Dec. 15, 1942 FOREIGN PATENTS NH:

Number Country Date where R, R and R" are lower alkyl groups. 294,085Germany Sept. 13, 1916

1. AN AMINO COMPOUND HAVING A FORMULA OF THE CLASS CONSISTING OF
 2. ANAMINO COMPOUND HAVING THE FORMULA